Theoretical explanation of the low-lying ν(6) vibrational fundamental of the FSO3 radical by the linear vibronic coupling approach

• Published in: The Journal of chemical physics 2013-06, Vol.138 (23), p.234307-234307
• Main Authors: Uhlíková, Tereza, Urban, Štěpán
• Format: Article
• Language: English
• ISSN: 1089-7690
• DOI: 10.1063/1.4810800

The first attempt for a theoretical explanation of the ν6 fundamental energy levels of the fluorosulfate radical (FSO3) electronic ground state has been made. The vibronic interaction of the two lowest electronic states of the radical (X̃ (2)A2 and à (2)E) has been taken into consideration in the basis of the linear vibronic coupling (LVC) approximation. The strengths of the intrastate and interstate vibronic couplings have been calculated within the framework of the Köppel, Domcke, and Cederbaum (KDC) model Hamiltonian. Already this simple KDC-LVC model provides the ν6 fundamental energy, which is in very good agreement with the experimental results. From the inclusion of vibronic interactions such as the pseudo-Jahn-Teller and Jahn-Teller effects into the calculation of the fundamental energy of the ν6 mode, it can be said that mainly the interstate coupling with the electronic excited state E causes the unexpectedly low fundamental energy ν6 of the FSO3 radical.